3,3′′-Bis(9-hy­droxy­fluoren-9-yl)-1,1′:3′,1′′-terphen­yl

Konstantinos Skobridis; Vassiliki Theodorou; Georgios Paraskevopoulos; Wilhelm Seichter; Edwin Weber

doi:10.1107/S1600536813024033

. 2013 Sep 7;69(Pt 10):o1514–o1515. doi: 10.1107/S1600536813024033

3,3′′-Bis(9-hydroxyfluoren-9-yl)-1,1′:3′,1′′-terphenyl

Konstantinos Skobridis ^a, Vassiliki Theodorou ^a, Georgios Paraskevopoulos ^a, Wilhelm Seichter ^b, Edwin Weber ^b,^*

PMCID: PMC3790384 PMID: 24098206

Abstract

The asymmetric unit of the title compound, C₄₄H₃₀O₂, contains two independent molecules in which the terminal rings of the terphenyl element are inclined at angles of 36.3 (1) and 22.5 (1)° with respect to the central ring and the dihedral angles between the fluorenyl units are 72.3 (1) and 62.8 (1)°. In the crystal, pairs of O—H⋯O hydrogen bonds link the molecules into inversion dimers. The hydroxy H atoms not involved in these hydrogen bonds form O—H⋯π interactions in which the central terphenyl rings act as acceptors. Weak C—H⋯O contacts and π–π [centroid–centroid distance = 4.088 (2) Å] stacking interactions also occur. Taking into account directed non-covalent bonding between the molecules, the crystal is constructed of supramolecular strands extending along the a-axis direction.

Related literature

For the preparation of the starting material for the synthesis of the title compound, see: Staab & Binnig (1967 ▶). For background to organic solid-state inclusion chemistry, see: Atwood et al. (1991 ▶). For the design strategy of host compounds, see: Desiraju (1996 ▶). For diol host inclusion complexes, see: Toda (1996 ▶). For host compound 2,2′-bis(9-hydroxy-9-fluorenyl)biphenyl, see: Weber et al. (1993 ▶); Skobridis, Paraskevopoulos et al. (2011 ▶); Skobridis, Theodorou et al. (2011 ▶). For weak O—H⋯π and C—H⋯O interactions, see: Desiraju & Steiner (1999 ▶). For π–π stacking interactions, see: James (2004 ▶). graphic file with name e-69-o1514-scheme1.jpg

Experimental

Crystal data

C₄₄H₃₀O₂
M _r = 590.68
Triclinic,
a = 11.2292 (3) Å
b = 12.4823 (3) Å
c = 24.4440 (5) Å
α = 76.070 (1)°
β = 78.080 (1)°
γ = 66.917 (1)°
V = 3034.99 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 150 K
0.32 × 0.18 × 0.06 mm

Data collection

Bruker X8 APEXII CCD diffractometer
55787 measured reflections
13774 independent reflections
9930 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.109
S = 1.03
13774 reflections
845 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▶); cell refinement: SAINT (Bruker, 2007 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813024033/rk2410sup1.cif

e-69-o1514-sup1.cif^{(50.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813024033/rk2410Isup2.hkl

e-69-o1514-Isup2.hkl^{(673.3KB, hkl)}

Click here for additional data file.^{(11.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813024033/rk2410Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C20–C25 and C20A–C25A rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.86 (1)	2.07 (1)	2.894 (2)	163 (1)
O2—H2⋯Cg1ⁱⁱ	0.84 (1)	3.42 (1)	4.163 (2)	150 (1)
O1A—H1A⋯O2A ⁱⁱⁱ	0.85 (1)	1.99 (1)	2.807 (2)	160 (1)
O2A—H2A⋯Cg2^iv	0.85 (2)	3.46 (1)	4.169 (2)	145 (1)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) .

Acknowledgments

We thank the NMR Center and Mass Spectrometry Unit of the University of Ioannina for measuring the ¹H NMR and HRMS spectra. KS thanks the State Scholarships Foundation (IKY) for supporting this work.

supplementary crystallographic information

1. Comment

In the realm of organic state inclusion chemistry (Atwood et al., 1991), bulkily substituted diols have proven a versatile design strategy for the formation of host compounds (Desiraju, 1996) yielding crystalline host-guest complexes with a variety of guest molecules (Toda, 1996). With regard to that, 2,2'-bis(9-hydroxy-9-fluorenyl)biphenyl is a prototype host structure (Weber et al., 1993; Skobridis, Paraskevopoulos et al., 2010; Skobridis, Theodorou et al., 2011). Following this structural approach, the title compound involving exchange of the central 2,2'-disubstituted biphenyl unit for a 3,3"-disubstituted m-terphenyl moiety was prepared and its crystal structure studied unexpectedly showing a solvent-free crystal species on crystallization from ethanol. The compound was found in the space group P1 with two crystallographically independent molecules in the asymmetric unit (Fig. 1). The twist angles between the aromatic rings of their terpenyl element are 36.3 (1)° (rings A/B), 22.5 (1)° (rings B/C), 33.8 (1)° (rings A'/B') and 17.2° (rings B'/C') while the mean planes of the fluorenyl units are inclined at angles of 72.3 (1)° and 62.8 (1)°, respectively. The crystal structure (Fig. 2 & Fig. 3) is constructed of inversion dimers which are stabilized by classical O–H···O hydrogen bonds. The hydroxy H atoms excluded from strong hydrogen bonding interlink the molecular dimers via O–H···π interactions (Desiraju & Steiner, 1999) with the central rings of the terphenyl units acting as acceptors (O2–H2···C22 = 2.692 (2) Å, 153.3 (1)°; O2A–H2A···C22A = 2.724 (2) Å, 142.5 (1)°). Weak C–H···O contacts (Desiraju & Steiner, 1999) and π–π stacking interactions (James, 2004) (Cg(B)···Cg(B)ⁱ, 4.088 (2) Å; symmetry code: (i) 1-x, 2-y, 2-z) complete the pattern of intermolecular interactions.

2. Experimental

The starting compound 3,3"-dibromo-1,1':2',1"-terphenyl was prepared according to a literature procedure (Staab & Binnig, 1967). To a stirred solution of this dibromide (2.13 g, 5.5 mmol) in dry diethyl ether (25 ml), n-BuLi (1.6 N in n-hexane, 7.0 ml, 12 mmol) was added dropwise at 195 K under argon. Stirring of the mixture was continued at 253 K for 15 min. Then, fluorenone (1.98 g, 11.0 mmol) in 25 ml of dry diethyl ether was added and the mixture kept at reflux. After completion of the reaction (24 h), which was monitored by TLC (hexane/ethyl acetate 2:1, R_f 0.55), the mixture was cooled, quenched with saturated NH₄Cl solution and extracted with diethyl ether (2 × 30 ml). The combined organic extracts were dried (Na₂SO₄) and evaporated. The pale yellow oily residue was precipitated by the addition of hexane and purified by flash chromatography on a SiO₂ column (hexane/ethyl acetate 2:1) to yield 3.90 g (65 %) of a colourless solid. M.p. = 485-487 K. IR (KBr) 3446, 3037, 1597, 1467, 1448, 1166, 1120, 769, 738. ¹H NMR (500 MHz, CDCl₃) δ 2.61 (s, br, 2 H, OH), 7.34-7.62 (m, 21 H, ArH), 7.79-7.92 (m, 7 H, ArH). ¹³C NMR (125 MHz, CDCl₃) δ 83.7 (CO), 120.2, 124.3, 124.7, 124.8, 126.3, 128.5, 128.7, 129.0, 129.2, 139.7, 141.2, 141.8, 143.8. 150.4 (Ar). MS (HR-ESI) m/z: found 613.2126 [M+Na], calc. for C₄₄H₃₀O₂ + Na: 613.2138. The melting point (uncorrected) was measured on a hot stage microscope. The IR spectrum was recorded on a Perkin Elmer FT-IR 1600 spectrometer. ¹H and ¹³C NMR spectra were measured on a Bruker Avance AV-500 spectrometer using (CH₃)₄Si as internal standard. The high resolution ESI mass spectrum was obtained using a ThermoFisher Scientific Orbitrap XL spectrometer. Crystals of the title compound suitable for X-ray structural analysis were grown by slow evaporating a solution of the material in ethanol.